Polynitro nitraza diamines



United States Patent ice 1; 2 r and dropping funnel was placed a solution of 69.5 (0.38 mole) of 2,2,2-trinitroethanol and 250 m1. of

2,973,505 water, and a solution of 47.0 gm. (0.19 mole) of 3,6- POLYNITRO NITRAZA DIAMINES dinitraza-1,8-octane diamine dihydrochloride in 250- ml.

5 of water. A solution of 15.3 gm. (0.38 mole) of sodium Milton B. Frankel, Pasadena, and Karl Klager, Monrovia, hydroxide and 100, m1 of water was added dropwise eatit atares'tfsrz a A bright -w precipitated WhlCh after drying under vacuum exhibited No Drawing. Filed Apr. 13, 1956, Ser. No. 578,151 0 a M.P. of IOU-105 C., with decomposition.

. 1 ClallIlS- (Cl. 260--583) EXAMPLE II Preparation of 1,1,1,6,11,11,]1-Heptanitr0-3,6,9-Triaza- This invention relates to new compositions. 0t matter undecane useful as high explosives and a method for their preparai tion. In particular, this. invention. relates to polynitro In a flask fi t d w a m al r t m meter nitraza diamines having the general formula: and dropping funnel was placed 22.1 gm. (0.1 mole) of N 2 L In l IQa wherein A is an alky-lene radical andn is a small whole 3-.nitraza,-1, 5.-pentane diamine dihydrochloride, 3.6.2 gm. number from 0 to 1 inclusive. (0.2 mole) of 2,2,2-trinitroethanol and 75 ml. of water.

This application is a continuation-in-part of our co- A solution of 8 gm. (0.2 mole) of soduim hydroxide and pending United States patent application Serial. No. 416,- 50 ml. of water was added at room temperature. A yel- 699, filed March 16, 1954, now abandoned. low gummy solidprecipitated.

The compounds of this invention are prepared by con- We have also found that nitraza diamines such as 3,5- densing 2,2,2-trinitroethanol with a nitraza diamine, in dinitratza-lJ-heptane diamine and 3,8-dinitraza-1,10-deaccordance with. the general. reaction scheme: set forth cane. diamine readily: condense; with 2,2,2-trinitroethanol below: to produce the corresponding nitrazasecondary; diarnines,

wherein A and n: are as defined above. 40 namely; 1,1,1,6,8,13,13,13-octanitro-3,6,8,1l tetrazo-tri- Duev to the degration of trinitromethyl groups by decane and 1,1,1,6,11-,16,16,16-octanitro-3,6,l1,14-tetrazastrong alkalis, it is. preferred to conduct the condensation h d a at a pH. in the range O m about 4 to about AS It is apparent that any member of this series of polythe mtraza diamines are somewhat unstable tree bases, nitro nitraza diamines maybe prepared by merely select- Prefer to mtwduc? the dlammes mto reacqon ing the appropriate nitraza diamine and condensing it mlxture as salts' Opnmum results were obtained with 2,2,2,-trinitroethanol, in accordance with the teacha readily hydrolyzable organic salt. Another equally suitable method is to generate the diaminefrom a mineral acid salt in situ with a hydroxide or lower alkanoic acid salt of an alkali. or alkaline earth metal. I

The nitraza diami-nes used as starting materials. in missile, pro ectile, rocket, or the. like, as the, ma 1n exthis invention are prepared by reacting a Strong mineral ploslve charge. An example of such a missile 1s d1sacid with a nitramino isocyanate obtained by reacting closed In United St tes Patent No. 2,470,162, lSSllfld May an acid halide with sodium azide. The acid halidesjare 17, 1949- one y Of uslllg the hlgii explosives 0f f obtained by condensing acrylonitrile with ammonia or a invention in a device such as that disclosed in United diamine, as disclosed in Organic Reactions, vol. V, page States Patent No. 2,470,162, is to pack the crystallineex;

' ings of this invention. 7 V

The compounds of this invention are useful as high explosives and can be used in any conventional explosive 79, and subsequently reacting the condensation product plosive in powder form into the Warhead of the missilewith nitric acid, hydrolyzing the product and then re- Alternatively, the crystals can be first pelletized and then acting it with-thionyl halide. packed; A charge thus prepared is suficiently insensio more fully illustrate this invention, the following tive to withstand the shock entailed in the ejection of a examples are presented. It is to be understood, however, She f a gun barrel or from a rocket launching tube Y i examples are presented P fi as a means of under the pressure developed from ignition of a propelillustration and are not intended to hmit the scope of the 1am Charge, and a be caused to explode on Operation invention in any I of an impact,- or time fuse-mechanism firing a detonating explosive such as lead azide or mercury fulminate. Preparation of 1,1,1,6,9,14,]4,14-0ctanitr0-3,6,9,12- w claim; V 7

tetmza'tet-mdemne I 1. As compositions of matter, the polynitro nitraza di- In a flask fitted with a mechanical stirrer, thermometer amines having the general formula:

No, No, N0 7 no. N0 -(!7-OHz-NHC HzQH9N----.-Ar-N. -.--.QHZGHZ.NHOHZ 1T, }IQ;. I r ..L NO:

4 wherein A is a lower alkylene radical and n is a small whole number from to 1 inclusive, said nitraza diamine whole number from O to l inclusive. being generated in the reaction mixture from its mineral 2. As a composition of matter, 1,1,l,6,9,14,14,l4-octaacid salt by introducing a base selected from the group nine-3,6,9,IZ-tetraZa-tetradecane having the structural consisting of the hydroxides of alkali and alkaline earth formula: 5 metals. 1T0 IITO: 1T0: IIO: N0,-c-cH=-NH-oHioHrN-cHicHrN-(JHroHrNH-cHro-Nm N03 N02 3. As a composition of matter, l,l,1,6,11,11,11-hepta- 9. The method of preparing 1,1,1,6,9,l4,l4,l4-octaninitro-3,6,9-triaza-undecane having the structural formula: tro-3,6,9,IZ-tetraza-tctradecane which comprises condense N01 IITO: N03 Nor-c-cH,NH0HoHN-c110Hr-NH-cHr-cN0= 4. As a composition of matter, l,l,l,6,8,l3,l3,l3-octaing 3,6-dinitraza-1,8-octane diamine with 2,2,2-trinitr0- nitro-3,6,8,ll-tetraza-tridecane having the structural forethanol. mula: 10. The method of preparing 1,l,1,6,9,14,l4,14-octani- I110: IITO: lTTO: 1:101 NO:?CHz-NH-CH1OHz-NCHz-NCH:CH:NHCH:(f-N0 N07 N09 5. As a composition of matter, 1,1,1,6,l1,16,16,16-octatro-3,6,9,l2-tetraza-tetradecane which comprises condensnitro-3,6,l1,14-tetraza-hexadecane having the structural ing 2,2,2-trinitroethanol with 3,6-dinitraza-l,8-octane diformula: amine at a pH of from about 4 to about 8.

ITO: I110: 11101 N O: N0, o-cHr-NH0HioHr-N- 3H=0Hr0H=0H,N-cH,cHr-NHCHr-q-N0i NO: 1110: 6. The method of preparing polynitro nitraza diamines 11. The method of preparing l,1,l,6,9,14,14,14-octanihaving the general formula: tro-3,6,9,IZ-tetraZa-tetradecane which comprises condens- 11101 1Y0: lTTOe '1 N0: NOz(l3-CHr-NH-CHzCHzN --AN CHrCHr-NH-CHz-(']JNO1 NO: I- In No g g g gg gz ig f ig g a gigiigf wlth a ing 2,2,2-trinitroethanol with 3,6-dinitraza-l,8-octane dir g g amine dihydrochloride in the presence of sodium hydrox- NH=-o11;0HiN--- ---a-N- CHzOHr-NH: 12. The method of preparing 1,1,1,6,l1,11,1 1-heptani tro -3,6,9-triaza-undecane which comprises condensing 3- wherein A 15 a lower alkylene radical and n is a small nitrazwlipentane diamine with 2,2,24rinitmethanoL whole number from 0 to 1 mcluswe' 13. The method of preparing 1,l,l,6,l1,11,ll-heptani- 7. The method of preparing polynitro nitraza diamines a having the general formula: V tro 3,6,9 triaza undecane which comprises condensing N 0: Igor NO; "I NOg-l-CHz-NH-CHzCHr-N --A-N CHzCH -NH-CHz-(iJ-NO;

NO: I. n N02 which comprises condensing 2,2,2-trinitroethanol with a 2,2,2-n'initroethanol with 3-nitraza-l,5-pentane diaminc nitraza diamine having the general formula: at a pH of from about 4 to about 8.

14. The method of preparing 1,1,1,6,1l,1 1,11-heptani- 1 1 l tro-3,6,9-triaza-undecane which comprises condensing NHr-CHCHFL I: A N CECE-NH 2,2,2-trinitroethanol with 3-nitraza-1,5-pentane diamine 11 dihydrochloride in the presence of sodium hydroxide.

wherein A is a lower alkylene radical and n is a sma 15. The method of preparing 1,1,l,6,8,13,l3,13-octamwhole number from 0 to l inclusive; at a pH of from about 4 to about tro-3,6,8,1l-tetraza-tridecane which comprises condensing 8. The method of preparing polynitro nitraza diamines 2,2,2-trinitroethano1 with 3,5-dinitraza-l,7-heptane dihaving the general formula: amine. NO| r m, No, 1 :0, NO -(iJ-ClL-NH-CECH -N AN------- CH CH -NE-CIh-C-NO;

No; L N03 which comprises condensing 2,2,2-trinitroethanol with a .16. The method of preparing 1,1,l,6,ll.16 .l6,l6-octaninitraza diamine having the general formula: tro-3,6,l1,14-tetraza-hexadecane which comprises condensing 2,2,2-trinitroethanol with 3,8-dinitraza-L10-dec- NHr-CHaCHz-N----[--A-N----J- CHzCHr-NH:

wherein A is a lower alkylene radical and n is a small No references cited. 

1. AS COMPOSITIONS OF MATTER, THE POLYNITRO NITRAZA DIAMINES HAVING THE GENERAL FORMULA: 